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Spectroscopic and Computational Characterizations of Alkaline‐Earth‐ and Heavy‐Metal‐Exchanged Natrolites
Author(s) -
Liu Dan,
Chen Xin,
Ma Yanming,
Liu Zhenxian,
Vogt Thomas,
Lee Yongjae
Publication year - 2014
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201402114
Subject(s) - alkaline earth metal , chemistry , raman spectroscopy , metal , alkali metal , molecule , ring (chemistry) , infrared spectroscopy , ion , crystallography , synchrotron , analytical chemistry (journal) , physics , organic chemistry , optics , chromatography , nuclear physics
Synchrotron infrared (IR) and micro‐Raman spectra of natrolites containing alkaline‐earth ions (Ca 2+ , Sr 2+ , and Ba 2+ ) and heavy metals (Cd 2+ , Pb 2+ , and Ag + ) as extra‐framework cations (EFCs) were measured under ambient conditions. Complementing our previous spectroscopic investigations of natrolites with monovalent alkali metal (Li + , Na + , K + , Rb + , and Cs + ) EFCs, we establish a correlation between the redshifts of the frequencies of the 4‐ring and helical 8‐ring units and the size of the EFCs in natrolite. Through ab initio calculations we have derived structural models of Ca 2+ ‐ and Ag + ‐exchanged natrolites with hydrogen atoms, and found that the frequency shifts in the HOH bending mode and the differences in the OH stretching vibration modes can be correlated with the orientations of the water molecules along the natrolite channel. Assuming that the members of a solid solution series behave as an ideal mixture, we will be able to use spectroscopy to probe compositions. Deviation from ideal behavior might indicate the occurrence of phase separation on various length scales.